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Properties of 2D asynchronous spectra generated from a series of fluorescence emission spectra are investigated. Variable excitation wavelengths are utilized as an external perturbation. Based on the results of mathematical analysis and computer simulation, we find that no cross peak will be produced on the 2D asynchronous spectrum if the fluorescent solute under investigation occurs in a single micro-environment. The observation of cross peaks implies that the fluorescent molecule may occur in different micro-environments in a solution. Based on these results, we use 2D asynchronous spectra to investigate the emission spectra of anthracene dissolved in cyclohexane. When the concentration of anthracene is low, no cross peak is produced in the resultant 2D asynchronous spectrum, confirming that anthracene is dissolved as single molecule in the solution. As the concentration elevated, cross peaks appear in the corresponding 2D asynchronous spectra. A plausible explanation of this phenomenon is that anthracene may undergo aggregation via π-π interaction or π-C-H interaction.

We propose a substantially simplified approach to construct a pair of 2D asynchronous spectra based on the DAOSD approach proposed in our previous papers. By using a new concentration series, only three 1D spectra are used to generate a pair of 2D correlation spectra together with two reference spectra. By using this method, the previous problem of labor intensive traditional DAOSD approach has been successfully addressed. We apply the new approach to characterize intermolecular interaction between acetonitrile and butanone dissolved in carbon tetrachloride. The existence of intermolecular interaction between the two solutes can be confirmed by the presence of a cross peak in the resultant 2D IR spectra. In addition, the absence of cross peak around (2254, 2292) in Psi(butanone) provides another experimental evidence to reveal the intrinsic relationship between the stretching band and an overtone band (delta(CH3)+v(C-C)). (C) 2016 Elsevier B.V. All rights reserved.

The spectral behavior of a pair of 2D asynchronous spectra generated by using the double asynchronous orthogonal sample design (DAOSD) approach on a chemical system is investigated. Two solutes (P and Q) are dissolved in the solution and intermolecular interaction between P and Q is characterized. In this particular system, P occurs in two exchangeable states when it is dissolved in the solutions. Results on mathematical analysis and computer simulation demonstrated that interference unrelated to the intermolecular interaction can be completely removed. Hence the resultant 2D asynchronous spectra generated by using the DAOSD approach can reflect intermolecular interaction reliably. Moreover, properties of cross peaks in different regions of the pair of asynchronous spectra are discussed. In our previous works, cross peaks generated by using the DAOSD and relevant techniques reflect variations on peak position, bandwidth or absorptivity of the characteristic peaks of solutes caused by intermolecular interaction. However, we find that cross peak can still be produced even if intermolecular interaction do not bring about any changes on the characteristic peaks of solutes. Mathematical analysis demonstrates that cross peaks are related to the variations of chemical systems caused by intermolecular interaction at a network level.

We applied a newly developed technique of the DAOSD (Double Asynchronous Orthogonal Sample Design) approach to probe weak coordination between Co2+ ions and acetone. Subtle spectral variation on the carbonyl band of acetone and d-d transition band are revealed via cross peaks of 2D asynchronous spectra generated by using the DAOSD approach. These results suggest that coordination occur between cobalt ions and the carbonyl group of acetone. To confirm whether coordination occur between cobalt ions and acetone, EXAFS experiments are utilized. The EXAFS results reveal that a Co2+ is coordinated by six methanol molecules in anhydrous COCl2/methanol solution. Upon addition of acetone in into the anhydrous COCl2/methanol solution, the coordination number of Co2+ ion becomes four, and one coordinating oxygen atom is replaced by a chlorine atom. We infer that the decrease in coordination number of Co2+ ion is due to the participation of the carbonyl oxygen of acetone in the coordination since the size of acetone is larger than methanol. This result provides an alternative evidence to support the conclusion that Co2+ ions coordinate with acetone, which is separately obtained from the 2D asynchronous spectra generated by using the DAOSD approach. (C) 2014 Elsevier B.V. All rights reserved.